Solid titanium catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for olefin polymerization

ABSTRACT

Disclosed is a catalyst for olefin polymerization comprising [I] a solid titanium catalyst component [S] comprising titanium, magnesium, halogen and an electron donor (b), which is obtained by bringing a solid adduct consisting of a magnesium compound and an electron donor (a) into contact with an electron donor (b) and a liquid titanium compound by at least one method selected from (A) a method of contacting the materials in a suspended state in the coexistence of an inert hydrocarbon solvent and (B) a method of contacting the material plural times individed portions and [II] an organometallic compound catalyst component [M] containing a metal selected from the groups I to III in the periodic table.

TECHNICAL FIELD

The present invention relates to a solid catalyst component, a catalystand a polymerization process for producing a homopolymer or copolymer ofethylene and an α-olefin.

BACKGROUND ART

A catalyst comprising a titanium compound carried on a magnesium halidein, an active state, is known as a catalyst for use in the production ofolefin polymers such as a homopolymer of ethylene or an α-olefin and anethylene/α-olefin copolymer.

As the catalyst for olefin polymerization (hereinafter, “the catalystfor polymerization” is used sometimes to encompass “catalyst forcopolymerization”), a solid-titanium catalyst component comprisingmagnesium, titanium, halogen, and an electron donor, and anorganometallic compound is known.

This catalyst has a high activity, in polymerization or copolymerizationof α-olefins such as propylene, and butene-1, similar to polymerizationof ethylene (hereinafter, “polymerization” is used sometimes toencompass “copolymerization”), and the stereospecificity of theresulting polymer (hereinafter, “polymer” is used sometimes to encompass“copolymer”.) is also high.

Among these catalysts, a catalyst using a solid titanium catalystcomponent having an electron donor selected from carboxylates typicallyphthalates carried there on, an aluminum-alkyl compound as a catalystcomponent, and a silicon compound having at least one Si—OR bond (R is ahydrocarbon group) is known to exhibit excellent performance.

The present inventors have made investigations for the purpose ofobtaining a catalyst for olefin polymerization more excellent inpolymerization activity and stereoregularity, and as a result, theyfound that this object can be achieved by a catalyst using a specificsolid titanium catalyst component having magnesium, halogen, titaniumand an electron donor (b), and an organometallic compound, or by acatalyst comprising a specific solid titanium catalyst componentcomprising magnesium, titanium, halogen and an electron donor (b), anorganometallic compound, and, an electron donor (c).

DISCLOSURE OF INVENTION

The present invention was made under these circumstances, and the objectof the present invention is to provide a solid titanium catalystcomponent for olefin polymerization obtained by using a specificelectron donor by a specific preparation method, as well as an olefin(co)polymer having high stereospecificity with a high catalytic activityby (co)polymerization reaction of olefins by using the solid titaniumcatalyst component.

The solid titanium catalyst component [S] for olefin polymerizationaccording to the present invention comprising titanium, magnesium,halogen and an electron donor (b) is obtained by bringing a solid adductconsisting of a magnesium compound and an electron donor (a) intocontact with an electron donor (b) and a liquid titanium compound. Thisis accomplished either by (A) a method of contacting the materials in asuspended state in the coexistence of an inert hydrocarbon solvent or by(B) a method of contacting the materials plural times in dividedportions.

In the solid titanium catalyst component for olefin polymerizationaccording to the present invention, a compound having two or more etherlinkages can be used as the electron donor (b) to obtain a catalyst forolefin polymerization that can produce a polymer having highstereospecificity with sufficiently high activity without further, usingan electron donor in preparing the polymerization catalyst

When the particle diameter of the solid titanium catalyst component forolefin polymerization according to the present invention, is in therange of 30 to 150 μm a problem with fluidity of particles causing ahindrance in operation by adhesion of the particles, to a polymerizer inproducing block copolymers can be reduced.

The catalyst for olefin polymerization according to the presentinvention comprises a solid titanium catalyst component [S] containingtitanium, magnesium, halogen and an electron donor (b), and an organicmetal compound catalyst component [M] containing a metal selected fromthe groups I to III in the periodic table, the solid titanium catalystcomponent [S] being obtained by bringing a solid adduct consisting of amagnesium compound and an electron donor (a) into contact with anelectron donor (b) and a liquid titanium compound. This may beaccomplished either by (A) a method of contacting the materials in asuspended state in the coexistence of an inert hydrocarbon solvent or by(B) a method of contacting the materials plural times in dividedportions.

The process for olefin polymerization according to the present inventioncomprises polymerizing or copolymerizing at least one olefin selectedfrom ethylene and C₃₋₂₀ α-olefins by using the catalyst for olefinpolymerization described above.

In the catalyst for olefin polymerization and the process for olefinpolymerization according to the present invention, the organometalliccompound catalyst component [M] can be used together with the solidtitanium catalyst component [S] in the present invention to carry outthe polymerization reaction efficiently with a high catalytic activityto give a polymer having high stereospecificity.

In the catalyst for olefin polymerization and the process for olefinpolymerization according to the present invention, the catalystcomprising a specific electron donor (c) can be used in addition to thetwo components, that is, the solid titanium catalyst component [S] andthe organometallic compound catalyst component [M] to give a polymerhaving further higher stereoregularity.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the solid catalyst component for olefin polymerization, thecatalyst for olefin polymerization, and the process for olefinpolymerization according the present invention are described in detail.

The solid titanium catalyst component [S] for olefin polymerizationaccording to the present invention is obtained by bringing a solidadduct consisting of a magnesium compound and an electron donor (a) intocontact with an electron donor (b) and a liquid titanium compound by atleast one method selected from (A) a method of contacting the materialsin a suspended state in the coexistence of an inert hydrocarbon solventand (B) a method of contacting the materials plural times in dividedportions.

That is, the solid titanium catalyst component [S] for olefinpolymerization according to the present invention is classified into thesolid titanium catalyst component [S1] to [S3], depending on the methods(P-1) to (P-3), of contacting the electron donor (b) with a liquidtitanium compound.

The solid titanium catalyst component, [S1] obtained by the method.(P-1) of bringing a solid adduct consisting of a magnesium compound andthe electron donor (a) into contact with the electron donor (b) and aliquid titanium compound by a method (A) of contacting the materials ina suspended state in the coexistence of an inert hydrocarbon solvent.

The solid titanium catalyst component [S2] obtained by the method (P-2)of bringing a solid adduct consisting of a magnesium compound and theelectron donor (a) into contact with the electron donor (b) and a liquidtitanium compound by a method (B) of contacting the materials pluraltimes in divided portions.

The solid titanium catalyst component [S3] obtained by the method (P-3)of bringing a solid adduct consisting of a magnesium compound and theelectron donor (a) into contact with the electron donor (b) and a liquidtitanium compound by a method (A) and (B) of contacting the materials ina suspended state in the coexistence of an inert hydrocarbon solvent andcontacting the materials plural times in divided portions.

The catalyst for olefin polymerization according to the presentinvention comprises the solid titanium catalyst component [S] mentionedabove.

Hereinafter, the magnesium compound as a starting material of the solidadduct and the electron donor (a) in the present invention aredescribed, and then the method of preparing the solid adduct, and thesolid adduct thus obtained are described.

Then, the titanium compound as a starting material of the solid titaniumcatalyst component [S] and the electron donor (b) will be described. Asthe electron donor (b), an electron donor (b1) and an electron donor(b2) will be described respectively.

Then, the insert hydrocarbon solvent used in preparation of the solidtitanium catalyst component [S1], the method of preparing the solidtitanium catalyst component [S1], and the method of contacting thematerials plural times individed portions to produce the solid titaniumcatalyst component [S2] will be described.

Then, the organometallic compound catalyst component [M] will bedescribed, and finally the process for olefin polymerization by usingthe catalyst for olefin polymerization according to the presentinvention, and the electron donor (c) used if necessary in thepolymerization, will be described.

[Magnesium Compound]

The solid adduct used in preparation of the solid titanium catalystcomponent [S] used in the present invention is formed from a magnesiumcompound and the electron donor (a), and the magnesium compoundincludes, for example, magnesium halides such as magnesium chloride,magnesium bromide, magnesium iodide and magnesium fluoride;alkoxymagnesium halides such as methoxymagnesium chloride andethoxymagnesium chloride; aryloxymagnesium halides such asphenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium,isopropoxymagnesium, butoxymagnesium and 2-ethylhexoxymagnesium;aryloxymagnesium such as phenoxymagnesium; and magnesium carboxylatessuch as magnesium laurate and magnesium stearate.

These magnesium compounds maybe used alone or in combination thereof.These magnesium compounds maybe used as a complex or a binuclear complexwith another metal or a mixture with another metal compound.

Among, these, magnesium halides, particularly magnesium chloride, are,preferably used. The magnesium compound may be derived from anothermaterial.

[Electron Donor (a)]

As the electron donor (a), a compound having an ability to solubilizethe magnesium compound is used. The compound having an ability tosolubilize the magnesium compound is preferably an alcohol, an aldehyde,an amine, a carboxylic acid or a mixture thereof.

The alcohol having an ability to solubilize the magnesium compoundincludes, for example, aliphatic alcohols such as methanol, ethanol,propanol, butanol, ethylene glycol, methylcarbitol, 2-methylpentanol,2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol anddodecanol, alicyclic alcohols such as cyclohexanol andmethylcyclohexanol, aromatic alcohols such as benzyl alcohol andmethylbenzyl alcohol, and aliphatic alcohols containing an alkoxy group,such as n-butyl cellosolve.

The carboxylic acid includes C7 or more organic carboxylic acids such ascaprylic acid and 2-ethylhexanoic acid. The aldehyde includes C7 or morealdehydes such as capric aldehyde and 2-ethylhexyl aldehyde.

The amine includes C6 or more amines such as heptyl amine, octyl amine,nonyl amine, lauryl amine and 2-ethylhexyl amine. The electron donor (a)is preferably an alcohol, particularly preferably ethanol, propanol orbutanol.

[Method of Preparing the Solid Adduct]

The solid adduct used in preparing the solid titanium catalyst component[S] can be prepared by contacting the magnesium compound with theelectron donor (a). The solid adduct is preferably a complex prepared bycontacting magnesium chloride with an alcohol.

In preparing the solid adduct, the amounts of the magnesium compound andthe electron donor (a) used are varied depending on their type andcontact conditions, but usually the magnesium compound is used in anamount of 0.1 to 20 moles/L, preferably 0.5 to 5 moles/L per unit volumeof the electron donor (a).

[Titanium Compound]

The liquid titanium compound used in preparing the solid titaniumcatalyst component [S] in the present invention includes tetravalenttitanium compounds represented by the formula:Ti(OR)_(g)X_(4-g)wherein R is a hydrocarbon group, X is a halogen atom, and g satisfiesthe relationship of 0≦g≦4. Particular examples of such titaniumcompounds include titanium tetrahalides such as TiCl₄, TiBr₄ and TiI₄;alkoxytitanium trihalides such as Ti(OCH₃)Cl₃, Ti(OC₂H₅)Cl₃,Ti(O-n-C₄H₉)Cl₃, Ti(OC₂H₅)Br₃ and Ti(O-iso-C₄H₉)Br₃; alkoxytitaniumdihalides such as Ti(OCH₃)₂Cl₂, Ti(OC₂H₅)₂Cl₂, Ti(O-n-C₄H₉)₂Cl₂ andTi(OC₂H₅)₂Br₂; alkoxytitanium monohalides such as Ti(OCH₃)₃Cl,Ti(OC₂H₅)₃Cl, Ti(O-n-C₄H₉)₃Cl and Ti(OC₂H₅)₃Br; and tetraalkoxytitaniumssuch as Ti(OCH₃)₄, Ti(OC₂H₅)₄, Ti(O-n-C₄H₉)₄, Ti(O-iso-C₄H₉)₄ andTi(O-2-ethylhexyl)₄.

Preferable among these is titanium tetrahalide, particularly preferablytitanium tetrachloride. These titanium compounds may be used alone or inthe form of a mixture thereof.

[Electron Donor (b)]

In the solid titanium catalyst component [S] according to the presentinvention, the electron donor (b) is used in addition to theabove-described compound. The electron donor (b) which can be used inthe present invention includes the electron donor (b1) having two ormore ether linkages via a plurality of atoms and the other electrondonor (b,2), and in the:present invention, the electron donor (b1) isused preferably for the reason of higher polymerization activity.Hereinafter, the electron donors (b1) and (b2) are described.

[Electron Donor (b1)]

The electron donor (b1) having two or more ether linkages via aplurality of atoms is a compound having a plurality of atoms between atleast two ether (C—O—C) linkages, that is, between C—O—C and C—O—C.Specifically, the compound (b1) is a compound wherein at least two ether(C—O—C) linkages are linked via a plurality of atoms that are carbon,silicon, oxygen, sulfur, phosphorus or boron atoms or two or more kindsof atoms selected therefrom.

The atoms linking these ether linkages can have one or moresubstituent(s) containing at least one element selected from carbon,hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron andsilicon. The compound is preferably a compound wherein one or tworelatively highly bulky substituent(s) is (are) bound to an atom betweenether linkages, and the atoms linking the ether linkages contain aplurality of carbon atoms.

The compound having two or more ether linkages includes, for example,compounds represented by the formula (1):

wherein n is an integer satisfying the relationship of 2≦n≦10, and eachof R¹ to R²⁶ is a substituent having at least one element selected fromcarbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boronand silicon, and arbitrary groups in R¹ to R²⁶, preferably R¹ to R^(2n),may be combined together to form a ring other than a benzene ring, andthe main chain may contain atoms other than carbon.

The compound having two or more ether linkages described above includes,for example:

-   2-(2-ethylhexyl)-1,3-dimethoxypropane,-   2-isopropyl-1,3-dimethoxypropane,-   2-butyl-1,3-dimethoxypropane,-   2-s-butyl-1,3-dimethoxypropane,-   2-cyclohexyl-1,3-dimethoxypropane,-   2-phenyl-1,3-dimethoxypropane,-   2-cumyl-1,3-dimethoxypropane,-   2-isopropyl-2-isobutyl-1,3-dimethoxypropane,-   2-(2-phenylethyl)-1,3-dimethoxypropane,-   2-(2-cyclohexylethyl)-1,3-dimethoxypropane,-   2,2-dicylohexyl-1,3-dimethoxypropane,-   2,2-diethyl-1,3-dimethoxypropane,-   2,2-dipropyl-1,3-dimethoxypropane,-   2,2-dibutyl-1,3-dimethoxypropane,-   2-methyl-2-propyl-1,3-dimethoxypropane,-   2-methyl-2-benzyl-1,3-dimethoxypropane,-   2-methyl-2-ethyl-1,3-dimethoxypropane,-   2-methyl-2-isopropyl-1,3-dimethoxypropane,-   2-methyl-2-phenyl-1,3-dimethoxypropane,-   2-methyl-2-cyclohexyl-1,3-dimethoxypropane,-   2-methyl-2-isobutyl-1,3-dimethoxypropane,-   2,2-diisobutyl-1,3-dimethoxypropane,-   2,2-diphenyl-1,3-dimethoxypropane,-   2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,-   2,2-diisobutyl-1,3-diethoxypropane,-   2,2-diisobutyl-1,3-dibutoxypropane,-   2-isobutyl-2-isopropyl-1,3-dimethoxypropane,-   2,2-di-s-butyl-1,3-dimethoxypropane,-   2,2-di-t-butyl-1,3-dimethoxypropane,-   2,2-dineopentyl-1,3-dimethoxypropane,-   2-isopropyl-2-isopentyl-1,3-dimethoxypropane,-   2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,-   2,3-diphenyl-1,4-diethoxybutane,-   2,3-dicyclohexyl-1,4-diethoxybutane,-   2,3-dicyclohexyl-1,4-diethoxybutane,-   2,3-diisopropyl-1,4-diethoxybutane,-   2,4-diphenyl-1,5-dimethoxypenhtane,-   2,5-diphenyl-1,5-dimethoxyhexane,-   2,4-diisopropyl-1,5-dimethoxypentane,-   2,4-diisobutyl-1,5-dimethoxypentane,-   2,4-diisoamyl-1,5-dimethoxypentane,-   1,2-diisobutoxypropane,-   1,2-diisobutoxyethane,-   1,3-diisoamyloxyethane,-   1,3-diisoamyloxypropane,-   1,3-diisoneopentyloxyethane,-   1,3-dineopentyloxypropane,-   1,2-bis(methoxymethyl)cyclohexane,-   3,3-diisobutyl-1,5-oxononane,-   6,6-dibutyldioxyheptane,-   1,1-dimethoxymethylcyclopentane,-   2-methyl-2-methoxymethyl-1,3-dimethoxypropane,-   2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,-   2-cyclohexyl-2-methoxymethyl-1,3-dimethoxyprdpane,-   2,2-diisobutyl-1,3-dimethoxycyclohexane,-   2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane,-   2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,-   2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,-   2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane,-   2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,-   2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,-   2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,-   diphenylbis(methoxymethyl)silane,-   di-t-butylbis(methoxymethyl)silane, and-   cyclohexyl-t-butylbis(methoxymethyl)silane.

Preferable among these compounds are 1,3-diethers, particularly2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-7isopentyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane and2,2-bis-(cyclohexylmethyl)-1,3-dimethoxypropane.

[Electron Donor (b2)]

The solid titanium catalyst component [S] contained in the olefinpolymerization catalyst of the present invention may be prepared fromthe electron donor (b2) in place of the electron donor (b1) having twoor more ether linkages. The electron donor (b2) includes, for example,organic esters and organic acid anhydrides described in EP585869A1 filedby the present applicant.

The electron donor (b2) used is preferably a carboxylate, morepreferably a polyvalent carboxylate, and still more preferably aphthalate.

As described above, the electron donor (b) used in the present inventionis preferably the compound (b1) having two or more ether linkages via aplurality of atoms, more preferably a compound represented by theformula (1) above, particularly preferably 1,3-diethers. Particularlypreferable forms of such 1,3-diethers are described above. At the timeof preparation of the solid titanium catalyst component, a mixture ofthe electron donors (b1) and (b2) can also be used as the electron donor(b).

[Preparation of the Solid Titanium Catalyst Component [S1]]

The solid titanium catalyst component [S1] according to the presentinvention is prepared by bringing the solid adduct into contact with theelectron donor (b) and the liquid titanium compound in the coexistenceof an inert hydrocarbon solvent.

Hereinafter, several examples of preparation of the solid titaniumcatalyst component [S1] (also referred to hereinafter as “solid titaniumcomplex”) are described, but the present invention is not limited tosuch methods.

(P-a) The solid titanium complex is obtained by bringing the solidadduct into contact with the electron donor (b) in the coexistence of aninert hydrocarbon solvent, and then bringing the liquid titaniumcompound into contact with the resulting product.

(P-b) The solid titanium complex is obtained by bringing the solidadduct into contact with the liquid titanium compound in the coexistenceof an inert hydrocarbon solvent, and then brining the electron donor (b)into contact with the resulting product.

(P-c) The solid titanium complex is obtained by bringing the solidadduct into contact with the electron donor (b) and a halogen-containingcompound and/or an organometallic compound in the coexistence of aninert hydrocarbon solvent, and then bringing the liquid titaniumcompound into contact with the resulting product.

(P-d) The solid titanium complex is obtained by bringing the solidadduct into contact with the liquid titanium compound in the coexistenceof an inert hydrocarbon solvent, and then brining the electron donor (b)and a halogen containing compound and/or an organometallic compound intocontact with the resulting product.

The liquid titanium compound may be further contacted with the solidtitanium catalyst component [S1] obtained in the methods (P-a) to (P-d)described above.

The inert hydrocarbon solvent includes, for example, aliphatichydrocarbons such as propane, butane, pentane hexane, heptane, octane,decane, dodecane and kerosine, alicyclic hydrocarbons such ascyclopentane, cyclochexane and methylcyclopentane, aromatic hydrocarbonssuch aszbenzene, toluene and xylene, halogenated, hydrocarbons such asethylene chloride and chlorobenzene, or mixtures thereof.

Among these inert hydrocarbon solvents, aliphatic or aromatichydrocarbons are used preferably, and octane, decane, toluene and xyleneare used more preferably.

When the solid titanium catalyst component [S1] is prepared by thesemethods, the amounts of the solid adduct, the liquid titanium compoundand the electron donor (b) used are varied depending on their typecontacting conditions and contacting order, but preferably the electrondonor (b) is used in an amount of 0.01 to 5 moles, particularly 0.1 to 1mol, and the liquid titanium compound is used in an amount of 0.1 to1000 moles, particularly 1 to 200 moles, per mole of magnesium in thesolid adduct consisting of the magnesium compound and the electron donor(a). The inert hydrocarbon solvent is used preferably in an amount of0.0001 to 100 moles, particularly preferably 0.0001 to 0.1 mole.

The temperature for contacting these compounds is usually −70° C. to200° C., preferably −25° C. to 150° C.

The solid titanium catalyst component [S1] thus obtained containstitanium, magnesium and halogen and the electron donor (b).

In the solid titanium catalyst component [S1], the halogen/titaniumratio (atomic ratio) is 2 to 100, preferably 4 to 90, and when theelectron donor (b1) is used as the electron donor (b), the electrondonor (b1)/titanium ratio (molar ratio) is 0.01 to 100, preferably 0.2to 10, and, the magnesium/titanium ratio (atomic ratio) is 2to 100,preferably 4 to 50. On one hand, when the electron donor (b2) is used asthe electron donor (b), the electron donor (b2)/titanium ratio (molarratio) is 0.01 to 100, preferably 0.2 to 10, and the magnesium/titaniumratio (atomic ratio) is 2 to 100, preferably 4 to 50.

[Preparation of the Solid Titanium Catalyst Component [S2]]

The solid titanium catalyst component: [S2] in the present invention isprepared by contacting the solid adduct, the electron donor (b) and theliquid titanium compound with one another plural times individedportions. As the electron donor (b), the electron donors (b1) and (b2)can be used without limitation, but the electron donor (b1), that is,the compound having two or more ether linkages via a plurality of atoms,is used preferably as the electron donor (b) in order to achieve ahigher polymerization activity.

The method of preparing the solid titanium catalyst component [S2] isnot particularly limited, and this method is described by reference toseveral examples. In the present invention, “plural times” is defined astwo or more times, but in the following preparation examples (P-a′) to(P-d′), the materials are contacted twice. The compound having two ormore ether linkages is used as the electron donor (b)

(P-a′) The solid adduct is brought into contact with the compound havingtwo or more ether linkages and the solid titanium compound is broughtinto contact with the resulting product to give a solid titaniumcatalyst component precursor [S2′] and the solid titanium catalystcomponent precursor [S2′] is brought into contact again with thecompound having two or more ether linkages, and the liquid titaniumcompound is brought into contact again with the resulting product togive the solid titanium catalyst component [S2].

(P-b′) The solid adduct is brought into contact with the liquid titaniumcompound, and the compound having two or more ether linkages is broughtinto contact with the resulting product to give a solid titaniumcatalyst component precursor [S2′], and the solid titanium catalystcomponent precursor [S2′] is brought into contact again with the liquidtitanium compound, and the compound having two or more ether linkages isbrought into contact again with the resulting product to give the solidtitanium catalyst component [S2].

(P-c′) The solid adduct is brought into contact with the compound havingtwo or more ether linkages and a halogen-containing compound and/or anorganometallic compound, and the liquid titanium compound is broughtinto contact with the resulting product to give a solid titaniumcatalyst component precursor [S2′], and the solid titanium catalystcomponent precursor [S2′] is brought into contact again with thecompound having two or more ether linkages and a halogen containingcompound and/or an organometallic compound, and the liquid titaniumcompound is brought into contact again with the resulting product togive the solid titanium catalyst component [S2].

(P-d′) The solid adduct is brought into contact with the liquid titaniumcompound, and the compound having two or more ether linkages and ahalogen-containing compound and/or an organometallic compound broughtinto contact with the resulting product to give a solid titaniumcatalyst component precursor [S2′], and the solid titanium catalystcomponent precusor [S2′] is brought into contact again with the liquidtitanium compound, and the compound having two or more ether linkagesand a halogen-containing compound and/or an organometallic compound arebrought into contact again with the resulting product to give the solidtitanium catalyst component [S2].

The compound having two or more ether linkages may be further contactedwith the component obtained in the above methods (P-a′) to (P-d′).

When the solid titanium catalyst component [S2] is prepared by thesemethods, the amounts of the solid adduct, the liquid titanium compoundand the compound having two or more ether linkages are varied dependingon their type, contacting conditions, contacting order and contactingfrequency, but generally the total amount of the compound having two ormore ether linkages is used in an amount of 0.01 to 5 moles, preferably0.1 to 2.0 moles, more preferably 0.1 to 1.5 moles, per mole ofmagnesium in the solid adduct consisting of the magnesium compound andthe electron donor (a). When the materials are contacted twice, theamount of the compound having two or more ether linkages is morepreferably 0.1 to 1.0 mole in the first contact and 0.01 to 0.5. mole inthe second contact. The liquid titanium compound is used in an amount of0.1 to 1000 moles, particularly preferably 1 to 200 moles, per mole ofmagnesium in the solid adduct. The liquid titanium compound may be addedall at once or in divided portions. Usually, the liquid titaniumcompound may be added at the same time when the solid adduct or thesolid titanium catalyst component and the compound having two or moreether linkages are added individed portions.

The solid adduct is preferably used in a suspended state in ahydrocarbon solvent, and usually, its concentration (solidadduct)/(hydrocarbon solvent) is 1 to 1000 g/L, preferably 100 to 500g/L. The solid titanium catalyst component thus prepared corresponds tothe solid titanium catalyst component [S3] obtained by the contactingmethod (P-3) described above.

As the hydrocarbon solvent, the solvent used in preparation of the solidtitanium catalyst component [S1] can be used. Particularly, aliphatichydrocarbons such as octane and decane and aromatic hydrocarbon such astoluene and xylene are preferable.

In preparation of the solid titanium catalyst precursor [S2′], thetemperature for contacting the solid adduct, the liquid titaniumcompound, and the compound having two or more ether linkages as theelectron donor (b2) is usually −70° C. to 200° C., preferably −25° C. to150° C. The solid titanium catalyst component precursor [S2′] thusobtained contains titanium, magnesium, halogen and the compound havingtwo or more ether linkages.

The temperature at which the compound having two or more ether linkagesis further reacted with the solid titanium catalyst component precursor[S2′] obtained in the manner described above is usually −70° C. to 200°C., preferably −25° C. to 150° C. The compound having two or more etherlinkages is used in an amount of 0.01 to 5 moles, particularlypreferably 0.1 to 1 mole and the solid titanium catalyst component [S2]thus obtained contains titanium, magnesium, halogen and the compoundhaving two or more ether linkages.

In the solid titanium catalyst component [S2], the halogen/titaniumratio (atomic ratio) is 2 to 100, preferably 4 to 90, and the compoundhaving two or more ether linkages titanium ratio (molar ratio) is 0.01to 100, preferably 0.2 to 10, and the magnesium/titanium ratio (atomicratio) is 2 to 100, preferably 4 to 50.

The particle diameter of the solid titanium catalyst components [S1] and[S2] obtained by the methods described above is 30 to 150 μm, preferably30 to 100 μm, more preferably 30 to 80 μm. A particle diameter in thisrange is preferable because, for example, the fluidity of particlescausing a hindrance in operation by adhesion of the particles to apolymerizer in producing block copolymers can be improved.

The olefin polymerization catalyst according to the present inventioncomprises the solid titanium catalyst component [S] thus obtained and anorganometallic compound catalyst component [M] containing a metalselected from the groups I to III in the periodic table. Hereinafter,the organometallic compound catalyst component [M] is described in moredetail.

[Organometallic Compound Catalyst Component [M]]

The organometallic compound catalyst component [M] used includes, forexample, organoaluminum compounds, alkylated group I metal/aluminumcomplexes, and organometallic compounds of group II metals.

The organoaluminum compounds include, for example, organoaluminumcompounds represented by R^(a) _(n)AlX_(3-n) wherein R^(a) is a C₁₋₁₂hydrocarbon group, X is a halogen or hydrogen, and n is 1 to 3.

In the above formula, R^(a) is for example an alkyl group, cycloalkylgroup or aryl group, and examples thereof include a methyl group, ethylgroup, n-propyl group, isopropyl group, isobutyl group, pentyl group,hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenylgroup and tolyl group.

The organoaluminum compound includes the following compounds:trialkylaluminums such as trimethylaluminum, triethylaluminum,triisopropylaluminum and triisobutylaluminum; alkenylaluminums such asisoprenylaluminum; dialkylaluminum halides such as dimethylaluminumchloride and diethylaluminum chloride; alkylaluminum sesquihalides suchas methylaluminum sesquichloride and ethylaluminum sesquichloride;alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminumdichloride and isopropylaluminum dichloride; and alkylaluminum hydridessuch as diethylaluminum hydride and diisobutylaluminum hydride.

The organoaluminum compounds used include compounds represented by R^(a)_(n)AlY_(3-n) wherein R^(a) is as defined above, Y is a —OR^(b) group,—OSiR^(c) ₃ group, —OAlR^(d) ₂ group. —NR^(e) ₂ group, —SiR^(f) ₃ groupor —N(R^(g))AlR^(h) ₂ group, n is 1 to 2, R^(b), R^(c), R^(d) and R^(h)are each a methyl group, ethyl group, isopropyl group, isobutyl group,cyclohexyl group, phenyl group etc., R^(e) is hydrogen, a methyl group,ethyl group, isoptopyl group, phenyl group, trimethylsilyl group etc.,and R^(f) and R^(g) are each a methyl group, ethyl group etc.

Particular examples of such organoaluminum compounds include:R^(a) _(n)Al(OR^(b))_(3-n)  [i]

dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminummethoxide etc.R^(a) _(n)Al(OSiR^(c) ₃)_(3-n)  [ii]

Et₂Al(OSiMe₃)

(iso-Bu)₂Al(OSiMe₃)

(iso-Bu)-₂Al(OSiEt₃) etc.R^(a) _(n)Al(OAlR^(d) ₂)_(3-n)   [iii]

Et₂AlOAlEt₂

(iso-Bu)₂AlOAl(iso-Bu)₂ etc.R^(a) _(n)Al(NR^(e) ₂)_(3-n)  [iv]

Me₂AlNEt₂

Et₂AlNHMe

Me₂AlNHEt

-   -   Et₂AlN (Me₃Si)₂

(iso-Bu)₂AlN(Me₃Si)₂ etc.R^(a) _(n)Al(SiR^(f) ₃)_(3-n)   [v]

(iso-Bu)₂AlSiM₃ etc.R^(a) _(n)Al(N(R^(g))AlR^(h) ₂)_(3-n)   [vi]

Et₂AlN(Me)AlEt₂

(iso-Bu)₂AlN(Et)Al(iso-Bu)₂ etc.

In the above formulas, the term Et means an ethyl group, iso-Bu means anisobutyl group, and Me means a methyl group.

Preferable examples of such organoaluminum compounds includeorganoaluminum compounds represented by R^(a) ₃Al, R^(a)_(n)Al(OR^(b))_(3-n) and R^(a) _(n)Al(OAlR^(d) ₂)_(3-n).

The alkylated group I metal/aluminum complexes include, for example,compounds represented by the formula M¹AlR^(j) ₄ wherein M¹ is Li, Na orK, and R^(j) is a C₁₋₁₅ hydrocarbon group, and specifically LiAl(C₂H₅)₄,LiAl(C₇H₁₅)₄ etc. can be mentioned.

The organometallic compound of group II metals include compoundsrepresented by the formula R^(k)R¹M² wherein R^(k) and R¹ each representa C₁₋₁₅hydrocarbon group or a halogen and may be the same or differentprovided that the two are not simultaneously halogens, and M² is Mg, Znor Cd. Specifically, the organometallic compounds include diethylzinc,diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, andbutylmagnesium chloride.

These compounds can be used as a mixture thereof.

The amount of the organometallic compound catalyst component [M] used isdescribed in the item “Process for olefin polymerization” describedlater.

[Electron Donor (c)]

In the present invention, the above-described electron donors (b) and/orelectron donors (c) can be used if necessary with the organometalliccompound catalyst component [M]. The electron donor (c) is preferably anorganosilicon compound. This organosilicon compound includes, forexample, compounds represented by the formula:R_(n)Si(OR′)_(4-n)wherein R and R′ each represent a hydrocarbon group, and n satisfies therelationship of 0<n<4.

As the organosilicon compounds represented by the above formula,following compounds are exemplified; trimethylmethoxysilane,trimethylethoxysilane, dimethyldimethoxysilane, dimethylidiethoxysilane,diisbpropyldimethoxysilane, t-butylmethyldimethoxysilane,t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane,phenylmethyldimethoxysilane, dicyclohexyldimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,methyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,methyltrimethoxysilane, n-propyltriethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoXysilane,phenyltriethoxysilane, chlorotriethoxysilane, vinyltributoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,trimethylphenoxysilane, vinyltriacetoxysilane,dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane,2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane,tricyclopentylmethoxysilane, tricyclopentylethoxysilane,dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane,hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane,cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, andcyclopentyldimethylethoxysilane.

Among those preferably used are ethyltriethoxysilane,n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane,vinyltributoxysilane, diphenyldimethoxysilane,phenylmethyldimethoxysilane, dicyclohexyldimethoxysilane,cyclohexylmethyldimethoxysilane, phenyltriethoxysilane,dicyclopentyldimethoxysilane, hexenyltrimethox-ysilane,cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, andcyclopentyldimethylmethoxysilane.

These organosilicon compounds can be used as a mixture thereof.

When the above-described electron donors (b) and (c) are used ifnecessary with the organometallic compound catalyst component [M], theamount of the electron donors used is described in the following item“Process for olefin polymerization”.

[Process for Olefin Polymerization]

In the process for olefin polymerization according to the presentinvention, olefin polymerization is carried out using the catalyst forolefin polymerization according to the present invention.

In the process for olefin polymerization according to the presentinvention, the polymerization can also be carried out in the presence ofa prepolymerized catalyst obtained by prepolymerization of α-olefins inthe presence of the catalyst for olefin polymerization according to thepresent invention. This prepolymerization is carried out byprepolymerization of α-olefins in an amount of 0.1 to 1000 g, preferably0.3 to 500 g, particularly preferably 1 to 200 g, per g of the catalystfor olefin polymerization.

In the prepolymerization, the catalyst can be used at higherconcentration than the concentration of the catalyst in the system forthe succeeding polymerization.

In the prepolymerization, the concentration of the solid titaniumcatalyst component [S], in terms of titanium atom per L of liquidmedium, is usually in the range of about 0.001 to 200 mmol, preferablyabout 0.01 to 50 mmol particularly preferably 0.1 to 20 mmol.

The organometallic compound catalyst component [M] in prepolymerizationis used preferably in such an amount to form a polymer in an amount of0.1 to 1000 g, preferably 6.3 to 500 g, per g of the solid titaniumcatalyst component [S], and the amount of the catalyst component [M] isusually about 0.1 to 300 moles, preferably about 0.5 to 100 moles,particularly preferably 1 to 50 moles, per mole of titanium atom in thesolid titanium catalyst component [S].

In the prepolymerization, the electron donor (b) or the electron donor(c) such as an organosilicon compound can also be used if necessary, andthese components are used in an amount of 0.1 to 50 moles, preferably.0.5 to 30,moles, more preferably 1 to 10 moles, per mole of titaniumatom in the solid titanium catalyst component [S].

After olefins and the catalyst components are added to an inerthydrocarbon medium, the prepolymerization can be carried out undermoderate conditions.

The inert hydrocarbon medium used includes, for example, aliphatichydrocarbons such as propane, butane, pentane, hexane, heptane, octane,decane, dodecane and kerosine; alicyclic hydrocarbons such ascyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbonssuch as benzene, toluene and xylene; and halogenated hydrocarbons suchas ethylene chloride and chlorobenzene, or mixtures thereof.

Among these inert hydrocarbon mediums aliphatic hydrocarbons are usedparticularly preferably. When the inert hydrocarbon medium is used, theprepolymerization is carried out preferably in a batch system.

Alternatively, the prepolymerization can be carried out using the olefinitself as solvent or under substantially solvent-free conditions. Inthis case, the prepolymerization is carried out preferably continuously.

The olefin used in the prepolymerlization is preferably propylene andmay be identical with or different from the olefin used in thepolymerization described later.

The reaction temperature for prepolymerization is usually in the rangeof about −20° C. to 100° C., preferably −20° C. to 80° C., morepreferably 0 to 40° C.

In the prepolymerization, a molecular weight regulator such as hydrogencan also be used.

The prepolymerization is carried out desirably such that the polymer isformed in an amount of about 0.1 to 1000 g, preferably about 0.3 to 500g, more preferably 1 to 200 g, per g of the solid titanium catalystcomponent [S], as described above. When the amount of the polymer formedin the prepolymerization is too high, the efficiency of production ofthe olefin polymer may be lowered.

The prepolymerization can be carried out in a batch or continuoussystem.

Now, the polymerization carried out after the prepolymerization orwithout conducting the prepolymerization is described.

The olefin which can, be used in the polymerization includes ethyleneand C₃₋₂₀ α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene and 1-eicocene, among which propylene,1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene arepreferably used.

In the polymerization process of the present invention, these olefinsmentioned above can be used alone or as a mixture thereof. The startingmaterials usable together with ethylene and α-olefins include aromaticvinyl compounds such as styrene and allyl benzene; alicyclic vinylcompounds such as vinylcyclohexane; cyclic olefin such as cyclopentene,cycloheptene, norbornene, tetracyclododecene and compounds having theplural number of unsaturated bonds, for example conjugated ornon-conjugated dienes such as, isoprene and butadiene.

In the present invention, the prepolymerization and polymerization canbe carried out in either liquid phase polymerization such as solutionpolymerization and suspension polymerization or gaseous phasepolymerization.

When the polymerization is carried but in the reaction form of slurrypolymerization, the reaction solvent maybe the inert hydrocarbon used inthe prepolymerization or an olefin in a liquid state at the reactiontemperature.

In the polymerization process of the present invention, the solidtitanium catalyst component [S] is used usually in an amount of about0.0001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol. Further, theorganometallic compound catalyst component [M] is used usually in anamount of about 1 to 2000 moles, preferably about 5 to 500 moles, permole of titanium atom in the prepolymerized catalyst component in thepolymerization system. The electron donor (c) is used in an amount of0.001 to 50 moles, preferably 0.01 to 30 moles, more preferably 0.05 to20 moles, per mol of the organometallic compound catalyst component [M].

The molecular weight of the resulting polymer can be regulated by usinghydrogen in the polymerization, to give a polymer having a large meltflow rate.

In the polymerization in the present invention, the temperature forpolymerization of an olefin is usually about 20 to 100° C., preferablyabout 50 to 90° C., and the pressure is set usually at atmosphericpressure to 100 kg/cm², preferably at about 2 to 50 kg/cm². In thepolymerization process of the present invention, the polymerization canbe carried out in a batch, semi-continuous or continuous system.Further, the polymerization can also be carried out in two or more stepsunder different reaction conditions.

The olefinic polymer thus obtained may a homopolymer, a random polymeror a block copolymer.

Polymerization of an olefin, particularly propylene, using the catalystfor olefin polymerization described above gives a propylene polymerhaving an isotactic index (I.I.) of 70% or more, preferably 85% or more,particularly preferably 95% or more, expressed in terms of residuesextracted with boiling heptane.

The polymer has a lower Mw/Mn ratio indicative of molecular-weightdistribution determined by gel permeation chromatography (GPC) than thatof a polymer obtained by a conventional method, and the polymer havingan Mw/Mn ratio of 5 or less is generally obtained in the presentinvention.

In the present invention, the catalyst for olefin polymerization cancontain other components useful for olefin polymerization, in additionto the components described above.

EXAMPLE

Hereinafter, the present invention is described in more detail byreference to the Examples, but the present invention is not limited tothe Examples.

In the following examples, the bulk density and melt flow rate of thepropylene polymer, and the particle diameter of the solid titaniumcatalyst component, were measured by the following methods.

(1) Bulk density: Measured according to JIS K-6721.

(2) Melt flowrate (MFR): Measured according to ASTM D1238E (190° C.).

(3) Method of measuring the particle diameter of the solid titaniumcatalyst component [S]: Analyzed by centrifugal sedimentation using aCAPA-300 particle analyzer manufactured by Horiba, Ltd.

Example 1

(Preparation of Solid Titanium Catalyst Component [S1])

A high-speed stirring unit (Tokushukika Kogyo Co, Ltd.) having aninternal volume of 2 L was sufficiently purged with nitrogen and thencharged with 700 ml purified kerosine, 10 g commercially availablemagnesium chloride, 24.2 g ethanol and 3 g Emasol 320™ (sorbitandistearate, manufactured by Kao Atlas) and the temperature of the systemwas increased under stirring, and the mixture was stirred at 120° C. at800 rpm for 30 minutes. The reaction mixture under stirring at highspeed was transferred through a tube of Teflon (registered trademark)having an inner diameter of 5 mm to a 2-L glass flask (with a stirrer)containing 1 L purified kerosine previously cooled at −10° C. After thepurified solid was washed sufficiently with purified n-hexane byfiltration, a solid adduct having mole of magnesium chloride coordinatedwith 2.8 moles of ethanol was obtained.

The whole of the solid adduct, 46.2 mmol in terms of magnesium atom,suspended in 30 ml decane was introduced into 200 ml titaniumtetrachloride kept at −20° C. under stirring. This mixture was heated to80° C. over 5 hours, and when the temperature reached 80° C., 1.9 gdiisobutyl phthalate (DIBP) was added thereto, and the mixture washeated to 120° C. over 40 minutes. The mixture was kept at 120° C. for90 minutes under stirring.

After the reaction for 90 minutes was finished, solids were collected byhot filtration, and the solids were suspended again in 200 ml titaniumtetrachloride and heated, and when the temperature reached 130° C., themixture was maintained under stirring for 45 minutes.

After the reaction was finished, solids were collected again by hotfiltration and washed sufficiently with decane and hexane at 100° C.until a free titanium compound was no longer detected in the washingsolutions. The sold titanium catalyst component prepared in this mannerwas stored as decane slurry, and an aliquot thereof was dried for thepurpose of examining the catalyst composition.

The composition of the solid titanium catalyst component [S1] thusobtained was comprised of 2.4% by weight of titanium, 20% by weight ofmagnesium, 7.4% by weight of DIBP and 0.5% by weight of ethanolresidues. The particle diameter of the catalyst was 40 μm.

(Preparation of a Prepolymerized Catalyst)

Purified n-hexane, 100 ml, triethylaluminum, 3 mmol, and the solidtitanium catalyst component prepared in Example 1, 1.0 mmol in terms oftitanium atom, were introduced into a 200 mL four-necked glass reactorequipped with a stirrer, and then propylene was supplied for 1 hour at arate of 3.2 NL/h into the mixture at 20° C.

After the completion of feeding of propylene, the reactor was purgedwith nitrogen, and washing comprising removing a supernatant andintroducing purified n-hexane was conducted twice, and the resultingprepolymerized catalyst component was suspended again in purifiedn-hexane, and the whole of the suspension was transferred to a catalystbottle.

(Polymerization)

500 g propylene and 1 NL of hydrogen were introduced at room temperatureto a polymerization reactor with an internal volume of 2 L and thenheated, and triethylaluminum, 0.5 mmol, cyclohexylmethyldimethoxysilane(=CMMS), 0.1 mmol, and the prepolymerized catalyst component, 0.004 mmolin terms of titanium atom, were added thereto at 60° C., and thepolymerization reactor was kept at 70° C. After the polymerization wascarried out for 1 hour, the propylene was purged.

The yield was 23.7 g, and the polymer had an apparent bulk density of0.48 g/ml, an MFR of 3.9 dg/min., an I.I. of 98.4% and an activity of59.3 kg-PP/mmol-Ti.

Example 2

The same procedure as in Example 1 was repeated except that as theelectron donor (b), 2.3 g of 2-isobutyl-2isopropyl-1,3-dimethoxypropanewas used in place of DIBP. The composition of the solid titaniumcatalyst component thus obtained was comprised of 3.1% by weight oftitanium, 18% by weight of magnesium, 14.1% by weight of2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 0.9% by weight ofethanol residues. The particle diameter of the catalyst was 36 μm.

The same polymerization as in Example 1 was carried out except that theabove catalyst was used. The yield was 365 g, and the polymer had anapparent bulk density of 0.44 g/ml, an MRF of 12.0 dg/min., an I.I. of97.2%, and an activity of 91.1 kg-PP/mmol-Ti.

Example 3

The same procedure as in Example 1 was repeated except that as theelectron donor (b), 2.5 g of 2-isobutyl-2-isopentyl-1,3-dimethoxypropane was used in place of DIBP. The composition of the solid titaniumcatalyst component thus obtained was, comprised of 3.0% by weight oftitanium, 17% by weight of magnesium, 13.1% by weight of2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 0.8% by weight ofethanol residues. The particle diameter of the catalyst was 39 μm.

The same polymerization as in Example 1 was carried out except that theabove catalyst was used. The yield was 255 g, and the polymer had anapparent bulk density of 0.43 g/ml, an MRF of 11.0 dg/min., an I.I. of97.2%, and an activity of 128.0 kg-PP/mmol-Ti.

Example 4

The same procedure as in Example 1was repeated except that in preparingthe solid titanium catalyst component, 30 ml toluene was used in placeof 30 ml decane. The composition of the solid titanium catalystcomponent thus obtained was comprised of 2.4% by weight of titanium, 20%by weight of magnesium, 6.3% by weight of DIBP and 0.3% by weight ofethanol residues. The particle diameter of the catalyst was 42 μm.

The same polymerization as in Example 1 was carried out except that theabove catalyst was used. The yield was 313 g, and the polymer had anapparent bulk density of 0.45 g/ml, an MRF of 2.5 dg/min., an I.I. of98.4%, and an activity of 78.3 kg-PP/mmol-Ti.

Example 5

The same procedure as in Example 2 was repeated except that in preparingthe solid titanium catalyst component, 30 ml toluene was used in placeof 30 ml decane. The composition of the solid titanium catalystcomponent thus obtained was comprised of 3.2% by weight of titanium, 18%by weight of magnesium, 13.4% by weight of2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 0.8% by, weight ofethanol residues. The particle diameter of the catalyst was 38 μm.

The same polymerization as, in Example 1 was carried out except that theabove catalyst was used. The yield was 157 g, and the polymer had anapparent bulk density of 0.44 g/ml, an MRF of 5.4 dg/min., an I.I. of98.0%, and an activity of 78.5 kg-PP/mmol-Ti.

Example 6

The same procedure as in Example 1 was repeated except that when theprepolymerized catalyst obtained in Example 1 was used in thepolymerization, cyclohexylmethyldimethoxysilane as the electron donor(c) was not used. The yield was 228 g, and the polymer had an apparentbulk density of 0.44 g/ml, an MRF of 14.0 dg/min., an I.I. of 95.0%, andan activity of 114.0 kg-PP/mmol-Ti.

Comparative Example 1

The whole of the solid adduct prepared in Example 1, 46.2 mmol in termsof magnesium atom, was introduced in the solid form into 200 ml titaniumtetrachloride kept at −20° C. under stirring. The temperature of thismixed solution was increased over 5 hours to 80° C., and when thetemperature reached 80° C., 1.9 g of DIBP was added thereto, and thetemperature was increased over 40 minutes to 120° C. The temperature waskept at 120° C. for 90 minutes under stirring.

After the reaction for 90 minutes was finished, solids were collected byhot filtration, and the solids were suspended again in 200 ml titaniumtetrachloride and heated, and when the temperature reached 130° C., thistemperature was kept for 45 minutes under stirring.

After the reaction was finished, the solids were collected again by hotfiltration and washed with decane and hexane at 100° C. until a freetitanium compound was no longer detected in the washing solution. Thesolid titanium catalyst component prepared in this manner was stored asdecane slurry, and an aliquot thereof was dried for the purpose ofexamining the catalyst composition. The composition of the solidtitanium catalyst component thus obtained was comprised of 3.2% byweight of titanium, 17% by weight of magnesium, 13.8% by weight of DIBPand 0.5% by weight of ethanol residues. The particle diameter of thecatalyst was 40 μm.

The same polymerization as in Example 1 was carried out except that theabove catalyst was used. The yield was 163 g, and the polymer had anapparent bulk density of 0.48 g/ml, an MRF of 4.5 dg/min., an I.I. of98.2%, and an activity of 40.9 kg-PP/mmol-Ti.

Comparative Example 2

The same procedure as in Comparative Example 1 was repeated except thatas the electron donor (b), 2.3 g of2-isobutyl-2-isopropyl-1,3-dimethoxypropane was used in place of DIBP.The composition of the solid titanium catalyst component thus obtainedwas comprised of 4.1% by weight of titanium, 15% by weight of magnesium,18.2% by weight of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 0.9%by weight of ethanol residues. The particle diameter of the catalyst was38 μm.

The same polymerization as in Comparative Example 1 was carried outexcept that the above catalyst was used. The yield was 253 g, and thepolymer had an apparent bulk density of 0.43 g/ml, an MRF of 12.0dg/min., an I.I. of 97.1% and an activity of 63.3 kg-PP/mmol-Ti.

The above results are shown collectively in the following Table 1.

TABLE 1 Apparent Inert Electron Electron Activity bulk hydrocarbon donordonor Kg-PP/ I.I MFR density solvent (b) (c) mmol-Ti % dg/min g/mlExample 1 decane DIBP¹⁾ CMMS⁴⁾ 59.3 98.4 3.9 0.48 Example 2 decanediether A²⁾ CMMS 91.1 97.2 12.0 0.44 Example 3 decane diether B³⁾ CMMS128.0 97.2 11.0 0.43 Example 4 toluene DIBP CMMS 78.3 98.4 2.5 0.45Example 5 toluene diether A CMMS 78.5 97.2 5.4 0.44 Example 6 decanediether A none 14.0 95.0 14.0 0.44 Comparative none DIBP CMMS 40.9 984.5 0.48 Example 1 Comparative none diether A CMMS 63.3 97.1 12.0 0.43Example 2 ¹⁾Diisobutyl Phthalate²⁾2-Isobutyl-2-isopropyl-1,3-dimethoxypropane³⁾2-Isopropyl-2-isopentyl-1,3-dimethoxypropane ⁴⁾Cyclohexylmethyldimethoxysilane

Example 7

(Preparation of Solid Titanium Catalyst Component [S3])

A high-speed stirring unit (Tokushukika Kogyo Co., Ltd.) having aninternal volume of 2 L was sufficiently purged with nitrogen and thencharged with 700 ml purified kerosine, 10 g commercially availablemagnesium chloride,: 24.2 g ethanol and 3 g Emasol 320™ (sorbitandistearate, manufactured by Kao Atlas), and the temperature of thesystem was increased under stirring, and the mixture was stirred at 120°C. at 800 rpm, for 30 minutes. The reaction mixture under stirring athigh speed was transferred through a tube made of Teflon (registeredtrademark) having an inner diameter of 5 mm to a 2-L glass flask (with astirrer) containing 1 L purified kerosine previously cooled at −10° C.After solids generated were washed sufficiently with purified n-hexaneby filtration, a solid adduct having 1 mole of magnesium chloridecoordinated with 2.8 moles of ethanol was obtained.

The whole of the solid adduct, 46.2 mmol in terms of magnesium atom,suspended in 30 ml decane was introduced into 200 ml titaniumtetrachloride kept at −20° C. under stirring. This mixture was heated to80° C. over 5 hours, and when 80° C. was reached, 1.4 g2-isobutyl-2-isopropyl-1,3-dimethoxypropane was added thereto, and themixture was heated to 120° C. over 40 minutes. The mixture was kept at120° C. for 90 minutes under stirring.

After the reaction for 90 minutes was finished, solids were collected byhot filtration, and the solids were suspended again in 200 ml titaniumtetrachloride and heated, and when the temperature reached 130° C., 0.9g of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was added thereto, andthe mixture was maintained at 130° C. for 45 minutes under stirring.

After the reaction for 45 minutes was finished, solids were collectedagain by hot filtration, and the solids were suspended again in 200 mltitanium tetrachloride and heated, and when the temperature reached 130°C., the mixture was kept at this temperature for 45 minutes understirring. After the reaction finished, solids were collected again byhot filtration and washed sufficiently with decane and hexane at 100° C.until a free titanium compound was no longer detected in the washingsolution. The sold titanium catalyst component prepared in this mannerwas stored as decane slurry, and an aliquot thereof was dried for thepurpose of examining the catalyst composition.

The composition of the solid titanium catalyst component [S3] thusobtained was comprised of 2.7% by weight of titanium, 19% by weight ofmagnesium, 14.2% by weight of2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 0.2% by weight ofethanol residues. The particle diameter of the catalyst was 38 μm.

(Polymerization)

500 g of propylene and 1 NL of hydrogen were introduced at roomtemperature into a polymerization reactor with an internal volume of 2L, and then triethylaluminum, 0.5 mmol, cyclohexylmethyldimethoxysilane,0.1 mmol, and the solid titanium catalyst component [S3], 0.004 mmol interms of titanium atom, were added thereto, and the polymerizer wasrapidly heated to 70° C. After the polymerization was carried out at 70°C. for 1 hour, the reaction was terminated by a small amount ofmethanol, and the propylene was purged.

The yield was 446 g, and the polymer had an apparent bulk density of0.43 g/ml, an MRF of 10.5 dg/min, an I.I. of 97.3%, and an activity of112.0 kg-PP/mmol-Ti.

Example 8

(Preparation of Solid Titanium Catalyst Component [S3])

A catalyst was prepared in the same manner as in Example 7 except thatthe solid adduct, 54 mmol in terms of magnesium atom, was used.

(Polymerization)

The polymerization of propylene was carried out in the same manner as inExample 7 except for use of, the catalyst. The yield was 508 g, and thepolymer had an apparent bulk density of 0.43 g/ml, an MRF of 11.0dg/min., an I.I. of 97.3%, and an activity of 127.0 kg-PP/mmol-Ti.

Example 9

(Preparation of Solid Titanium Catalyst Component [S2])

A solid titanium catalyst component was prepared in the same manner asin Example 7 except that in preparing the solid titanium catalystcomponent in Example 7, decane was not used.

(Polymerization)

The polymerization of propylene was carried out in the same manner as inExample 7 except for use of the catalyst. The yield was 154 g, and thepolymer had an apparent bulk density of 0.42 g/ml, an MRF of 10.0dg/min, an I.I. of 97.3%, and an activity of 77.2 kg-PP/mmol-Ti.

Comparative Example 3

The whole of the solid adduct prepared in Example 7, 46.2 mmol in termsof magnesium atom, suspended in 30 ml decane was introduced into 200 mltitanium tetrachloride kept at −20° C. under stirring. This mixture washeated to 80° C. over 5 hours, and when 80° C. was reached, 2.3 g of2-isobutyl-2-isopropyl-1,3-dimethoxypropane was added thereto, and themixture was heated to 120° C. over 40 minutes. The mixture was kept at120° C. for 90 minutes under stirring.

After the reaction for 90 minutes was finished, solids were collected byhot filtration, and the solids were suspended again in 200 ml titaniumtetrachloride and heated, and when 130° C. was reached, the mixture wasmaintained at this temperature for 45 minutes under stirring. After thereaction was finished, solids were collected again by hot filtration andwashed sufficiently with decane and hexane at 100° C. until a freetitanium compound was no longer detected in the washing solution.

The sold titanium catalyst component prepared in this manner was storedas decane slurry, and an aliquot thereof was dried for the purpose ofexamining the catalyst composition.

The composition of the solid titanium catalyst component thus obtainedwas comprised of 2.7% by weight of titanium, 18% by weight of magnesium,15.6% by weight of 2-isobutyl-2,-isopropyl-1,3-dimethoxypropane and 0.7%by weight of ethanol residues. The particle diameter of the catalyst was38 μm.

(Polymerization)

The polymerization of propylene was carried out in the same manner as inExample 7 except for use of the catalyst. The yield was 341 g, and thepolymer had an apparent bulk density of 0.4 g/ml, an MRF of 11.5dg/min., an I.I. of 97.2%, and an activity of 85.1 kg-PP/mmol-Ti.

Example 10

(Preparation of a Prepolymerized Catalyst)

Purified n-hexane, 100 ml, triethylaluminum, 3 mmol, and the solidtitanium catalyst component [S2] prepared in Example 7, 1.0 mmol interms of titanium atom, were introduced into a 200 mL four necked glassreactor equipped with a stirrer in a nitrogen atmosphere, and thenpropylene was supplied for 1 hour at a rate of 3.2 NL/h into the mixtureat 20° C.

After the completion of feeding of propylene, the reactor was purgedwith nitrogen, and washing comprising removing a supernatant andintroducing purified n-hexane was conducted twice, and the resultingprepolymerization catalyst component was suspended again in purifiedhexane, and the whole of the suspension was transferred to a catalystbottle.

(Polymerization)

500 g of propylene and 1 NL of hydrogen were introduced at roomtemperature to a polymerization reactor with an internal volume of 2 Land then heated to 60° C., and triethylaluminum, 0.5 mmol,cyclohexylmethyldimethoxysilane, 0.1 mmol, and the prepolymerizationcatalyst component, 0.004 mmol in terms of titanium atom, were addedthereto, and the polymerizer was rapidly heated to 70° C. After thepolymerization was carried out at 70° C. for 1 hour, the reaction wasterminated by a small amount of methanol, and the propylene was purged.The yield was 298 g, and the polymer had an apparent bulk density of0.46 g/ml, an MFR of 11.0 dg/min., an I.I. of 97.4%, and an activity of74.6 kg-PP/mmol-Ti.

The above results are shown collectively in Table 2.

TABLE 2 Number the Inert Activity Apparent materials hydro- Kg-PP/ MFRbulk were carbon mmol- I.I dg/ density contacted solvent Ti % min g/mlExample 7 2 Decane 112.0 97.3 10.5 0.43 Example 8 2 Decane 127.0 97.311.0 0.43 Example 9 2 None 77.2 97.3 10.0 0.42 Comparative 1 Decane 85.197.2 11.5 0.40 Example 3 Example 2 Decane 74.6 97.4 11.0 0.46 10¹⁾¹⁾Polymerization system using the prepolymerized catalyst.

As described above, the solid titanium catalyst component [S] of thepresent invention can be used to obtain a catalyst for olefinpolymerization having a higher catalytic activity and giving a polymerhaving high stereospecificity, without using an electron donor at thetime of polymerization. By simultaneously using the electron donor (c)at the time of polymerization, a catalyst for olefin polymerizationhaving a further higher catalytic activity and giving a polymer havinghigh stereospecificity can be produced.

The catalyst for olefin polymerization according to the presentinvention comprises the solid titanium catalyst [S] and anorganometallic compound catalyst component [M] containing a metalselected from the groups I to III in the periodic table, and the olefinpolymerization process of the present invention comprises polymerizationor copolymerization of a monomer selected from α-olefins by using thecatalyst for olefin polymerization. Accordingly, the catalyst for olefinpolymerization and the olefin polymerization process according to thepresent invention, polymerization reaction can be carried out highlyefficiently with a high catalytic activity to give a polymer having highstereospecificity.

1. A solid titanium catalyst component for olefin polymerization, saidcatalyst comprising titanium, magnesium, halogen, and an electron donor(b), which catalyst is obtained by bringing a solid adduct consisting ofa magnesium compound and an electron donor (a) into contact with anelectron donor (b) and a liquid titanium compound at one time or pluraltimes in divided portions by contacting the components of the catalystsuspended in an inert hydrocarbon solvent.
 2. A solid titanium catalystcomponent for olefin polymerization, said catalyst comprising titanium,magnesium, halogen, and an electron donor (b), which catalyst isobtained by bringing a solid adduct consisting of a magnesium compoundand an electron donor (a) into contact with an electron donor (b) and aliquid titanium plural times in divided portions by contacting thecomponents of the catalyst suspended without an inert hydrocarbonsolvent.
 3. The solid titanium catalyst component of claim 1, whereinsaid inert hydrocarbon solvent is an aliphatic hydrocarbon, an alicyclichydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, or amixture thereof.
 4. The solid titanium catalyst component of claim 1,wherein said inert hydrocarbon solvent is toluene.
 5. The solid titaniumcatalyst component for olefin polymerization according to claim 1 orclaim 2, wherein the electron donor (b) is a compound having two or moreether linkages.
 6. The solid titanium catalyst component for olefinpolymerization according to claim 1 or claim 2, whose particle diameteris 30 to 150 μm.
 7. A catalyst for olefin polymerization, comprising thesolid titanium catalyst component for olefin polymerization described inclaim 1 or claim 2 and an organometallic compound catalyst componentcontaining a metal selected from the groups 1 to 3 in the periodictable.
 8. A process for olefin polymerization, which comprisespolymerizing at least one olefin selected from the group consisting ofethylene and C₃₋₂₀ α-olefins by using the catalyst for olefinpolymerization described in claim 1 or claim 2.